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WO2015054703A1 - Revêtements amorphes polymères autoréparants assistés par mémoire de forme - Google Patents

Revêtements amorphes polymères autoréparants assistés par mémoire de forme Download PDF

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Publication number
WO2015054703A1
WO2015054703A1 PCT/US2014/064917 US2014064917W WO2015054703A1 WO 2015054703 A1 WO2015054703 A1 WO 2015054703A1 US 2014064917 W US2014064917 W US 2014064917W WO 2015054703 A1 WO2015054703 A1 WO 2015054703A1
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Prior art keywords
tba
coating
network
thermoplastic
samples
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Patrick T. Mather
Erika RODRIGUEZ
Xiaofan Luo
Sabrina CRANDALL
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to self-healing polymer systems and, more particularly, to a shape memory assisted self-healing polymer having improved optical qualities.
  • Microcrack formation and scratches contribute to the decline in visibility through optical lenses used in consumer and industrial products.
  • coatings are often used to protect the optical lenses.
  • the primary function of a coating is to protect sensitive surfaces from their environment.
  • eyeglasses made from polymeric materials, such as polycarbonate contain a built-in scratch-resistant coating and other additional coatings are commercially available for optical lenses, such as those used for anti-reflectance and anti-fog applications.
  • Scratch-resistant coatings may prolong the "life" of optical lenses; however, they can still be damaged in the same manner as unprotected glass or polycarbonate.
  • SMASH shape memory assisted self-healing
  • the present invention comprises an optical coating system made from a single amorphous phase having a network polymer component and a linear polymer component.
  • the network polymer component and the linear polymer component are miscible and each have a glass transition temperature between 25 degrees Celsius and 40 degrees Celsius.
  • the linear polymer component is inter-coiled within the network polymer component to form a semi-interpenetrating polymer network.
  • the network polymer component may be a tert-a butyl acrylate network formed from tert-a butyl acrylate cross-linked with tetrathyleneglycol dimethacrylate.
  • the linear polymer component may be a tert-butyl acrylate thermoplastic.
  • the single amorphous phase can range between 10 percent of the linear polymer and 90 percent of the network polymer by weight, 25 percent of the linear polymer and 75 percent of the network polymer by weight, and 50 percent of the linear polymer and 50 percent of the network polymer by weight.
  • the system may be used as a coating by binding the single amorphous phase to a substrate bound.
  • the substrate may comprise glass that is covalently bound to the single amorphous phase by silanization.
  • FIG. 1 is a schematic of an amorphous SMASH coating according to the present invention.
  • FIG. 2 is a series of representative optical micrographs of a coating according to the present invention in the virgin, damaged, and healed states;
  • Fig. 3 is a schematic of the preparation of the tBA thermoplastic (SH agent) synthesis through the thermal initiated free radical polymerization process;
  • Fig. 4 is a schematic showing the preparation of tBA SMASH films by UV initiated polymerization process with a representative image of a film to show the
  • Fig. 5 is a schematic of the silanization process on the glass substrate
  • Fig. 6 is a schematic showing preparation of tBA SMASH coating using a silanized glass slide with a representative image of a coating on a glass substrate to show the transparency;
  • Fig. 7 is a graph of gel permeation chromatography (GPC) showing the light scattering and refractive index (RI) traces needed to calculate the molecular weight (M w ) and number average molecular weight (M n ) for the Tert-butyl acrylate (tBA) thermoplastic;
  • GPC gel permeation chromatography
  • Fig. 8 is a graph showing the dependence of the l:n-tBA blend's gel fractions
  • Fig. 9 A is a representative thermogravimetric analysis (TGA) curves showing degradation temperatures where all l:n-tBA compositions and neat tBA thermoplastic were heated at 10 °C/min to 600 °C;
  • Fig. 9B is a graph showing onset degradation temperature vs. tBA
  • thermoplastic wt - % content for an average of three samples for each composition tested
  • Fig. 10A is a graph of the first heating traces of the exothermic peak indicating complete cure was not accomplished among the l:n-tBA systems;
  • Fig. 10B is a graph of the second heating revealing the T g transitions for all the compositions tested with no exothermic peak evident;
  • Fig. IOC is a graph of the first heating from samples that were post cured revealing complete cure and T g transitions with no exothermic peak evident;
  • Fig. 10D is a graph of the second heating from samples that were post cured revealing complete cure and T g transitions with no exothermic peak evident;
  • Fig. 11 is a graph showing the T g obtained from the second heating of the post cured l:n-tBA samples, where three samples were tested for each composition as a function of tBA thermoplastic wt - % content;
  • Fig. 12A is a graph of the representative traces showing tensile storage modulus ( ⁇ ') as a function of temperature among all l:n-tBA compositions tested;
  • Fig. 12B is a graph showing tensile storage modulus as a function of tBA thermoplastic content for three samples tested for each composition where standard error bars are shown and the tensile storage modulus was recorded at 25 °C, 60 °C, and 100 °C to observe the change in thermomechanical properties at these temperatures;
  • Fig. 13A is a reversible plasticity shape memory (RPSM) graph showing the l:n-tBA composition of 0: 100;
  • Fig. 13B is an RPSM graph showing the l:n-tBA composition of 10:90;
  • Fig. 13C is an RPSM graph showing the l:n-tBA composition of 25:75;
  • Fig. 13D is an RPSM graph showing the l:n-tBA composition of 50:50;
  • Fig. 14A is a representative RPSM graph for all l:n-tBA compositions tested as a function tBA thermoplastic content;
  • Fig. 14B is a graph of the fixing (R f ) and recovery (R r ) ratios for all l:n-tBA compositions tested as a function tBA thermoplastic content;
  • Fig. 15A is a one-way shape memory (1WSM) curve for 0: 100 l:n-tBA compositions where a 1mm thick rectangular specimen was thermally treated at 120 °C for 10 min and cooled at RT for 10 min prior to testing, with strain vs temperature in a back plane and stress vs strain curves on a side plane;
  • 1WSM shape memory
  • Fig. 15B is a 1WSM curve for 10:90 l:n-tBA compositions where a 1mm thick rectangular specimen was thermally treated at 120 °C for 10 min and cooled at RT for 10 min prior to testing, with strain vs temperature in a back plane and stress vs strain curves on a side plane;
  • Fig. 15C is a 1WSM curve for 25:75 l:n-tBA compositions where a 1mm thick rectangular specimen was thermally treated at 120 °C for 10 min and cooled at RT for 10 min prior to testing, with strain vs temperature in a back plane and stress vs strain curves on a side plane;
  • Fig. 15D is a 1WSM curve for 50:50 l:n-tBA compositions where a 1mm thick rectangular specimen was thermally treated at 120 °C for 10 min and cooled at RT for 10 min prior to testing, with strain vs temperature in a back plane and stress vs strain curves on a side plane;
  • Fig. 16 is a graph of the fixing (R f ) and recovery (R r ) ratios for all l:n-tBA compositions tested for 1WSM experiments;
  • Fig. 17 is a graph of showing transmittance vs wavelength to investigate the carbonyl group present on silanized glass slide using FTIR-ATR;
  • Fig. 18 is a graph showing self-healing efficiency as a function of tBA thermoplastic content among all l:n-tBA compositions tested;
  • Fig. 19 is a series of graphs showing the transmittance vs wavelength trend among the average of three samples tested for each l:n-tBA composition for coatings in their virgin, damaged and thermally treated states, with the following compositions shown: (a) (0: 100), (b) (10:90), (c) (25:75), and (d) (50:50);
  • Fig. 20 is a series of graphs showing transmittance vs wavelength for the l:n- tBA coatings in their virgin, damaged, and thermally treated states, where three (0: 100) samples were tested and (a) shows Run 1, (b) shows Run 2, and (c) shows Run 3;
  • Fig. 21 is a series of graphs showing transmittance vs wavelength for the l:n- tBA coatings in their virgin, damaged, and thermally treated states, where three (10:90) samples were tested and (a) shows Run 1, (b) shows Run 2, and (c) shows Run 3;
  • Fig. 22 is a series of graphs showing transmittance vs wavelength for the l:n- tBA coatings in their virgin, damaged, and thermally treated states, where three (25:75) samples were tested and (a) shows Run 1, (b) shows Run 2, and (c) shows Run 3.
  • the present invention comprises an amorphous, optically transparent, colorless shape memory assisted self-healing (SMASH) system that may be used as a coating for optical glassware applications.
  • SMASH shape memory assisted self-healing
  • the system employs a combination of surface shape memory and self-healing properties to repair damaged sites on glass substrates when exposed to a thermal stimulus.
  • the coating includes a miscible combination of a network polymer and a linear polymer having a T g between room temperature and about 40 degrees C. The shape memory phenomena of the coating are used for crack closure and the
  • a thin coating of the system may be applied as a liquid to a substrate and then cured by application of heat or ultraviolet light. Scratching of the coating (for example, by a razor blade) causes the creation of new surfaces due to cohesive failure as well as stored elastic energy (stress) due to compression of the crosslinked polymer. Heating of the coating leads to release of the stored energy while also tackifying the surfaces so that the crack closes and then rebonds until the damage is no longer evident.
  • the present invention thus takes advantage of the shape memory effect for crack closure and to provide a minimum amount of healing material needed for rebonding any damage, combined with self-healing effects to restore the optical characteristics of the coating as originally provided.
  • the system may be used as a coating for corrective eyewear, for windshields and windows in automobiles and motorcycles, as well for as optical coatings wherever needed.
  • the system comprises a single amorphous phase having a first network polymer component and a second linear polymer component.
  • first and second components may comprise any combination of network and linear polymers that are miscible and have a T g between room temperature and about 40 degrees C.
  • the network polymer component may comprise homopolymers and copolymers containing one or more of the following monomers combined to achieve a T g in the range 20 ⁇ T g ⁇ 40 °C: vinyl chloride, vinyl butyral, vinyl fluoride, vinyl pivalate, 2- vinylnaphthalene, 2-vinylpyridine, 4- vinyl pyridine, vinylpyrrolidone, n- vinyl carbazole, vinyl toluene, vinyl benzene(styrene), methyl methacrylate, ethyl methacrylate, acryl- functionalized POSS, methacryl-functionalized POSS, vinyl ethyl ether, vinyl laurate, vinyl methyl ether, vinyl propionate, alkyl acrylates, alkyl methacrylates, crosslinked with any multifunctional comonomer (polymerization functionality > 1), including ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, crosslinked with any multi
  • the linear polymer component may comprised of homopolymers and copolymers containing one or more of the following monomers combined to achieve a T g in the range 20 ⁇ T g ⁇ 40 °C and to be miscible with the network polymer: vinyl chloride, vinyl butyral, vinyl fluoride, vinyl pivalate, 2-vinylnaphthalene, 2-vinylpyridine, 4-vinyl pyridine, vinylpyrrolidone, n-vinyl carbazole, vinyl toluene, vinyl benzene(styrene), methyl methacrylate, ethyl methacrylate, acryl-functionalized POSS, methacryl-functionalized POSS, vinyl ethyl ether, vinyl laurate, vinyl methyl ether, vinyl propionate, alkyl acrylates, alkyl methacrylates.
  • These components may be combined by dissolution of the linear polymer into a liquid mixture of the network polymer monomers, crosslinker, and any polymerization initiator known in the art.
  • This miscible blend can be homogenized by stirring and application of heat. Once homogenized, the system can be applied to a coating and cured by application of light or heat.
  • the coating can be applied to a glass substrate via a three step process.
  • the first step is the silanization of the substrate.
  • the glass substrate Prior to silanization, the glass substrate is placed in a piranha solution comprised of sulfuric acid and hydrogen peroxide, which is heated for one hour (safety precautions are required for this cleaning step). This process hydrolyzes the surface of the glass, and removes organic impurities.
  • the substrate is then silanized using a solution of ethanol and deionized water acidified with acetic acid.
  • One percent by volume of (3- acryloxypropyl) trimethoxysilane is added and the substrate is placed in solution and agitated manually.
  • the substrate is then rinsed in fresh ethanol and the coupling agent cured in a convection oven. Silanization promotes better adherence of the polymer coating to the glass substrate and prevents delamination from occurring during damage.
  • the coating is fabricated, such as by making a solution of tert-butyl acrylate (tBA) monomer, butyl acrylate (BA) monomer, 2-2' azobisisobutyronitrile (AIBN), and triethylene glycol dimethyl acrylate (TEGDMA). This solution is stirred mechanically while a ShimStock 12 ⁇ thick spacer is cut.
  • the solution is syringed between the silanized substrate with the spacer in the middle and a RainX-treated glass substrate is placed on top.
  • the sample is secured together, such as by using binder clips along the edges, and is cured via ultra violet (UV) irradiation.
  • UV ultra violet
  • the SMASH coating may be evaluated, such as by scratch testing and subsequent heating to stimulate SMASH, to quantify healing.
  • testing of exemplary coatings has established the benefits of the present invention.
  • the coating prior to damaging, the coating is placed in its virgin state in a 120 °C convection oven for thermal history removal.
  • optical microscope images illustrate pre-damaged samples featuring damage produced by scratching the sample with a razor blade in a custom scratching machine, and then post-scratched samples after exposure to a thermal stimulus in a convection oven to reach the thermally treated state of the coating.
  • Self-healing efficiency may be measured by analyzing the optical micrographs using software, such as the ImageJ image processing program.
  • tBA tert-butyl acrylate
  • SH tBA self-healing
  • Tert-butyl acrylate, (tBA) monomer (98% pure) (molecular weight of 128.17 g/mol), Tetrathyleneglycol dimethacrylate (TEGDMA) crosslinker (molecular weight of 330.37 g/mol), and Azobisisobutyronitrile (AIBN) (98 % pure) photo initiator (molecular weight 164.21 g/mol) were purchased from Sigma Aldrich.
  • the tBA monomer contained 10-20 ppm monomethyl ether hydroquinone inhibitor in order to reduce the degree of polymerization, oxidation and darkening during storage.
  • a thermal initiated free radical polymerization process was conducted to synthesize tBA thermoplastic, which served as the SH agent for the SMASH system.
  • 10 mL (8.33 g) of tBA monomer and 0.083 g (1 wt-%) AIBN (photo initiator) were dissolved in 20 mL distilled toluene.
  • Toluene was used because it was miscible with the tBA monomer, has a high boiling point of 110 °C and also reduced the degree of the Trommsdorff effect
  • the reaction was conducted at 70 °C under nitrogen purge and constant magnetic stirring for 6 h.
  • the solution was precipitated using a BUCHI R - 210 rotary evaporator at 55 °C and rotated at a rate of 20 RPM. This step was conducted in order to extract the toluene from the solution.
  • the resulting viscous solution was dissolved in 30 mL anhydrous tetrahydrofuran (THF) followed by re-precipitation in a 150 mL methanol/150 mL water solution to yield the desired tBA thermoplastic.
  • THF anhydrous tetrahydrofuran
  • thermoplastic was left under the fume hood for 24 h to dry and was further dried for 24 h under vacuum at 45 °C.
  • Fig. 3 shows the tBA thermoplastic synthesis for a thermal initiated free radical polymerization process. TGA analysis was then conducted to confirm complete solvent removal and dryness of the thermoplastic. Gel Permeation Chromatography (GPC) analysis was conducted to determine number- average molecular weight (M n ), weight- average molecular weight (M w ) and polydispersity index (PDI). The values are reported in Table 1 below.
  • l-tBa:n-tBA films were made by forming the SM network through free radical polymerization in the presence of the synthesized tBA thermoplastic. This was done by crosslinking the tBA monomer with TEGDMA (5 wt-% of tBA monomer) where AIBN (1 wt-% of tBA monomer) formed free radicals to initiate the polymerization process.
  • the tBA thermoplastic was not covalently crosslinked with the shape memory network, but simply randomly inter-coiled within the network to form a semi-interpenetrating polymer network (SIPN).
  • SIPN semi-interpenetrating polymer network
  • a solution of tBA monomer, tBA thermoplastic, TEGDMA crosslinker, and AIBN photo initiator was prepared in a 20 mL vial and stirred at RT on a magnetic stirrer until the thermoplastic completely dissolved to make a homogeneous solution. No solvent was added to the solution as the thermoplastic powder dissolved in the presence of the tBA monomer. The solution was then syringed in a glass mold made of two 75 (1) x 25 (w) x 1 (th) mm glass slides where a 1 mm thick Teflon spacer was positioned in between the two glass slides and binder clipped together.
  • the glass slides were first pre-treated with RainX prior to syringing the solution to ensure the cured films did not adhere to the glass slides to prepare films (not coatings) for testing purposes.
  • Ultraviolet (UV) irradiation was then used for 1 h at RT to cure tBA SMASH films. This was done by placing the samples in an enclosed box that contained an upper and lower 60 W UV lamp with a wavelength of 352 nm in order to allow for uniform curing. Each sample was then removed from the glass molds and placed in individual bags.
  • Fig. 4 shows the preparation of the tBA SMASH systems via the UV initiated polymerization process.
  • the weight percentages (wt - %) of the tBA monomer and thermoplastic were varied to fabricate the following compositions (l-tBA wt _ % :n-tBA wt _ % ): 1- tBA 0 :n-tBA 10 o, l-tBA 10 :n-tBA 90 , l-tBA 25 :n-tBA 75 , and l-tBA 50 :n-tBA 5 o.
  • the wt- % were varied in order to optimize both the SM and SH effects.
  • G(%) is the gel fraction percentage
  • n3 ⁇ 4 is the initial dry weight before extraction
  • ⁇ 3 ⁇ 4 is the dry weight after extraction. This equation calculated the amount of SM network formed.
  • TGA Thermogravimetric Analysis
  • the samples were post cured at 120 °C for 10 min in a convection oven and cooled at RT for 10 min to completely cure. This was confirmed by running DSC before and after the post cure treatment. Each sample was then tested three times for reproducibility.
  • DMA Dynamic Mechanical Analyzer
  • Each sample was first heated to an equilibrium temperature of 120 °C to remove the thermal history, then ramped to -50 °C at 3 °C/min, held isothermally for 5 min, and finally heated to 120 °C at 3 °C/min.
  • the tensile storage modulus ( ⁇ ') of the second heating was reported.
  • Each sample of each composition was tested three times for statistical reproducibility.
  • the tensile storage modulus at 25 °C, 60 °C, and 100 °C were also reported to study the tensile storage modulus change as a function of temperature. These three temperatures were chosen to identify the thermomechanical properties during the following three states: glass at 25 °C, transition at 60 °C, and rubber at 100 °C.
  • RPSM shape memory polymers
  • R (N) g " ⁇ x l00% (2)
  • e m , e u , ⁇ ⁇ and N are the strain before unloading, the strain after unloading, permanent (unrecoverable) strain after shape recovery and the cycle number, respectively.
  • the samples were heated at 120 °C for 10 min and cooled at RT for 10 min prior to testing to remove the thermal history.
  • the sample was clamped in the DMA using tensile fixtures and heated to 80 °C, held isothermally for 1 min, and the strain was set to 0%.
  • the force was then ramped to 0.5 N/min until 40% strain was achieved in order to elastically deform the sample and then held isothermally for 2 min.
  • the temperature was then ramped from 80 °C to 0 °C at 3 °C/min, and held isothermally for 5 min in order to temporally fix this deformation.
  • the force was then ramped down to 0.001 N at 0.05 N/min and held for 2 min to observe the fixing properties of the sample.
  • the sample was finally heated back to 80 °C to complete the 1WSM cycle. Three cycles were conducted for each l-tBA:n-tBA system.
  • the fixing and recovery ratios were calculated using equation 2 and 3 defined in the previous section.
  • Silanization was conducted following the hydroxylation process by preparing a (95:5) solution of ethanol and deionized water (38 mL ethanol and 2 mL deionized water). The solution was acidified to pH 4 - 5 using acetic acid, which was added drop-wise and tested using pH paper. Acetic acid was introduced to prevent polymerization of the coupling agent. 1-% by volume (0.4 mL) (3-acryloxyproply) trimethoxysilane, 95-% was added drop wise to the solution while stirring with a glass rod at RT for 5 min. The glass slides were submerged and the bath was agitated in a circular manner for 5 min.
  • FTIR- ATR was conducted on non-silanized and silanized glass slides to evaluate the presence of the carbonyl group within the (3-acryloxyproply) trimethoxysilane coupling agent. FTIR- ATR was conducted in order to observe the presence of the carbonyl group.
  • 10 ⁇ thick coatings were prepared on optical surfaces. This was done by UV curing a l-tBA:n-tBA network on the chemically modified silanized glass substrate. The sample preparation and compositions detailed above were used to make coatings. The solution was syringed onto a silanized glass slide with a 10 ⁇ thick spacer, which was pre- cut from a ShimStock sheet to the height and width of the slide. A second, non-silanized slide was then placed on top, sandwiching the liquid. The second slide was treated with RainX to prevent coating-glass adhesion on that mold surface. The slides were secured together with binder clips. The coatings were then UV cured for 1 h as seen in Fig. 6. The non-silanized glass slide was then removed to expose the 10 ⁇ coating cured on the silanized glass substrate.
  • OM imaging was conducted using an Olympus BX-51 polarizing microscope and Q Capture Pro software. Prior to scratching, the coating was heated to 120 °C for 20 min and cooled at RT for 20 min to remove the thermal history. The OM was calibrated for proper light alignment and image focusing. An OM micrograph of the coating in its virgin state at lOx magnification was captured. The sample was then scratched using a razor blade in a custom built motorized scratching machine at RT. The coating was firmly fastened into the sample holder and placed on the movable track.
  • the track was connected to a motor that was attached to the back of the scratch machine.
  • the motor is connected to a controller via wires where the user has the option to move the track forward or backward depending on the direction of damage that is desired.
  • Each coating was scratched in a forward motion in order to form a uniaxial scratch where a track speed of 0.9 mm/sec was used.
  • a second OM micrograph was then taken of the scratched coating.
  • the damaged coating was then thermally treated by heating it in an isothermal oven at 120 °C for 20 min resulting in crack closure and healing through the SMASH effect.
  • the coating was then cooled at RT for 20 min where a final OM micrograph was taken. This process was repeated four times for each composition to study reproducibility.
  • OM images were used in evaluating the SH efficiency. This was done by importing all the OM micrographs in .TIFF format into the ImageJ software where in some cases the use of the paint tool to fill in the area of the scratch in black was performed for ease of analysis.
  • the .TIFF images were then converted to an 8-bit format and saved as a .bmp.
  • the images were then imported into Vision Assistant software, where the images were analyzed to obtain the area in pixels of the scratched and thermally treated coatings. This was done by making an analysis program containing a series of steps in the Vision Assistant software. First, a manual threshold on the images was conducted to isolate the area of the scratch (highlighted red) from the rest of the coating surface. The next step was to remove small objects from the image.
  • SH Efficiency (%) ⁇ r TTS xl00
  • Spectrometer studies were also carried out to quantify the transmittance of light through the virgin, damaged and thermally treated states of the coatings relative to a pristine glass surface.
  • an Ocean Optics, Inc. spectrometer was attached to the OM microscope.
  • OOIBase32 software was then used to analyze the percent transmittance of light through the coated glass at each of the states.
  • a dark reference consisting of a razor blade covering the light source, and a reference consisting of a pristine glass slide was stored, giving the software a baseline to compare the coated samples to.
  • a graph of transmittance vs wavelength was recorded for each composition. This process was conducted three times on each coating to obtain reproducibility.
  • thermoplastic was made via a thermal initiated free radical polymerization process to be used as the SH agent in the SMASH system.
  • the resultant thermoplastic after precipitation and drying step was a brittle, white, and porous material.
  • Fig. 7 shows the GPC data analysis for the light scattering and infrared traces, and Table 1 below shows the numerical values obtained to calculate the M n , M w , and PDI averages.
  • Degree of shape memory network formation was measured by gel fraction experiments. This was done by submerging small cured specimens of each composition in methanol and agitating for 24 h at 25 °C where each sample was weighed pre and post methanol extraction. Gel fractions were calculated using equation 1 above. All samples remained amorphous pre and post extraction where the samples expanded in volume in the methanol during the 24 h period. The sample volume expansion is due to solvent swelling of the tBA network. All samples remained intact during the swelling process.
  • Fig. 8 shows a linear relationship of gel fraction % as a function of tBA thermoplastic content where Table 2 below shows the gel fractions (G%) for the average of three samples tested among the four compositions made.
  • the G values show a decreasing trend with a decrease in network formation.
  • TGA analysis was conducted in order to examine the onset degradation temperatures of all compositions tested.
  • the onset degradation temperatures are important to analyze as the samples start to decompose and lose their structural and mechanical properties at the onset point.
  • Fig. 9A shows representative TGA curves of each compositions and neat tBA thermoplastic.
  • tBA monomer could not be analyzed using the TGA as it is a volatile liquid and cannot be accurately tested. It is hypothesized that the tBA monomer will evaporate completely prior to degradation.
  • There is a common trend among all the compositions and thermoplastic where the first weight drop indicates the onset degradation temperature ranging from 259 C° + 1.3 to 260 °C + 0.3 (Table 3) below for three samples tested.
  • the onset degradation temperature is hypothesized to be the tBA side chains degrading.
  • the increase in weight loss with the increase in temperature is hypothesized to be the backbone of the tBA polymer degrading.
  • Fig. 9B shows the onset degradation temperature vs. tBA thermoplastic wt-% content for an average of three samples tested. All onset temperatures were similar in magnitude which was as expected since the polymers used did not change among the compositions studied.
  • T g is an important polymer characteristic as it reveals the onset of chain molecular motion in polymeric systems and the onset for crack- closure during the SMASH process. This is where polymers transition from a hard glassy state to a rubbery state.
  • Fig. 10A shows representative curves of the first heating traces where an exothermic peak is evident. This peak suggests that all compositions cured for 1 h under UV exposure were not completely cured.
  • Fig. 10B shows the second heating of these same samples where the exothermic peak was no longer evident, but instead the T g 's were revealed ranging from 47 °C to 49 °C, as seen in Table 4 below.
  • Fig. IOC shows the first heating of the post cured samples showing the T g transitions only with no evidence of exothermic peaks. This means all samples that were post cured showed complete curing.
  • Fig. 10D shows the second heating of the post cured samples where these T g values were reported and are shown to have the same values as the as cured samples in the 2 nd heating trace.
  • Fig. 1 1 shows the average T g values of three samples tested as a function of tBA thermoplastic wt- %. Table 4 above shows the numerical values of the average T g 's with accompanying standard deviations.
  • T g values were approximately the same in magnitude regardless of composition. It was initially hypothesized that more crosslinking formed due to a higher monomer wt-% would increase the T g as more energy is required for polymer chain motion between crosslinks. This would mean that a higher thermoplastic content would lead to a lower T g . However, this was not an evident trend among these films studied.
  • Fig. 12A shows representative traces of the E' transitions as a function of temperature for each composition tested. Here, the onset T g and rubbery plateau is observed.
  • Fig. 12B shows the average E' as a function of tBA
  • thermoplastic wt - % content for three specimens tested at 25 °C, 60 °C and 100 °C. Table 5 below shows the average numerical values of E' with standard deviations.
  • the tBA SMASH system is able to sustain its geometry due to the crosslinks present in the tBA thermoset network.
  • the elimination of the crosslinks needed to form the network would result in the sample to flow.
  • RPSM was characterized to observe a new SM effect, reversible plasticity SM.
  • Figs. 12A through 12D show representative 3D RPSM graphs of l-tBA:n-tBa compositions.
  • the sample already in its vitrified state, is elastically and plastically deformed to achieve 30% strain (step 1 - 2) at RT, as seen in Fig. 12A.
  • the polymer chains are aligning in the direction of loading during deformation.
  • the sample is then unloaded to observe the fixing properties (step 2 -3), as seen in Fig. 12B. Rubber elasticity can be used to explain the polymer chain response.
  • the tBA polymer chains When the crosslinked polymer chains are at equilibrium, in its undeformed state, the tBA polymer chains are in a highly coiled entropic conformation. As the network is uni-axially stretched at RT to achieve 30% strain, the entropy is significantly reduced since the number of polymer conformations decreases. Upon force release, the polymer chains, which can be modeled as entropic springs, elastically recover. The sample is able to elastically recover due to the stored energy the sample gained during deformation. The specimen is then heated to 80 °C to observe the plastic deformation recovery for near complete shape recovery (step 3 - 4), as seen in Fig. 12A, of each specimen.
  • Fig. 12B shows a graph of strain vs. temperature to further convey the elastic and plastic deformation followed by shape recovery (black dashed line).
  • the side plane shows a stress vs strain to show the complete cycle in 2D (black solid line).
  • Figs. 12A through 12D show RPSM curves for (a) (0: 100), (b) (10:90), (c) (25:75), and (d) (50:50), respectively.
  • Fig. 13A shows representative RPSM curves for all compositions tested on one graph to compare each composition among each other. It can be observed that all samples regardless of tBA SH thermoplastic content can achieve 30% strain, demonstrate near complete fixing upon unloading and near complete shape recovery.
  • Fig. 13B shows a bar graph of the fixing (R f ) and recovery (R r ) ratios among all compositions tested as a function of thermoplastic wt-% content. Table 6 below shows the average Rr which ranged from 95.9 % to 97.8 % and R r of 83.6 % to 97.3 % among all compositions.
  • RPSM plays a critical role for surface damage on coatings because most damage incurred initiates below the coating's T g and therefore results in a significant amount of plastic deformation.
  • the RPSM effect shows that elastic and plastic deformation can occur and yet are reversible upon a thermal stimulus. This is critical as this recovery is necessary for scratch repair on coatings.
  • One Way Shape Memory (1WSM) was conducted on all compositions to observe a unique and different form of shape memory when compared to RPSM. Whereas the samples were stretched below their T g in RPSM, here the samples were first heated above their T g and then deformed, cooled to achieve temporal deformation and heated again for shape recovery.
  • Figs. 15A through 15D show the 1WSM for (0: 100), (10:90), (25:75), and (50:50) respectively. Each sample was heated to 80 °C where it was in its beginning point of the rubbery state and then elastically deformed to achieve 40% strain.
  • Fig. 16 shows a bar graph of the average R f and R r where Table 7 below shows the average R f ranging from 98.3% to 98.9 % and R r ranging from 91.7 % to 95.7 %.
  • Optical microscopy was carried out to measure the SH efficiency of each l:n-tBA coating by taking OM micrographs at three different coating stages: virgin, damaged, and thermally treated. The OM micrographs showed no evidence of coating-glass substrate delamination where a uniform degree of damage is observed. The SH efficiency was then calculated by comparing the area in pixels of the scratch and thermally treated coating. The average SH efficiencies of each composition are documented in Fig. 18 and Table 8 below, where the SH efficiency increased with increasing thermoplastic wt-% content.
  • Fig. 19 shows average transmittance (%) vs wavelength (nm) graphs of three samples in each composition.
  • Fig. 20 through Fig. 22 show all the raw transmittance (%) vs wavelength (nm) graphs for each of the four compositions where three tests were performed on each coating.
  • Table 9 below shows the average of the transmittance within the visible spectrum among four scratches analyzed.
  • This example outlines the fabrication and characterization of tBA SIPN single phase blends for optical applications.
  • Films were fabricated where thermal and thermo- mechanical analyses were conducted in order to observe the thermal transitions and viscoelastic properties as a function of temperature necessary for crack closure and healing. Scratch testing and spectrometer analysis were conducted on thin clear 12 ⁇ coatings to observe the SM and SH effect needed for scratch repair on coating surfaces. Transmittance studies were conducted pre and post damage and after thermal treatment where the l-tBA 5 o:n- tBA 50 composition proved to be the best system for optimum SM and healing for scratch repair.
  • Such SMASH coatings can be used for eye glassware, microscope lenses for industrial products as well as other applications where transparent SMASH coatings are needed for scratch repair and optimization of the coating composition for various application can be achieved by optimizing the T g .
  • the coating system features a self-healing mechanism capable of repairing microcracks, scratches, and other types of damage while retaining optical quality

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Abstract

L'invention porte sur un revêtement amorphe, incolore et optiquement transparent autoréparant assisté par mémoire de forme pour des applications d'articles optiques en verre, qui utilise une association de mémoire de forme de surface et de propriétés autoréparantes pour réparer des sites endommagés sur des substrats en verre lorsqu'ils sont exposés à un stimulus thermique. Le revêtement comprend une association miscible d'un polymère réticulé et d'un polymère linéaire ayant une température de transition vitreuse comprise entre la température ambiante et environ 40 °C. Le revêtement peut être utilisé pour la lunetterie corrective, pour des pare-brise et des fenêtres dans des automobiles et des cyclomoteurs, ainsi que pour des revêtements optiques partout où on en a besoin.
PCT/US2014/064917 2013-10-10 2014-11-11 Revêtements amorphes polymères autoréparants assistés par mémoire de forme Ceased WO2015054703A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017130152B3 (de) 2017-12-15 2019-01-03 Acquandas GmbH Verfahren zum Betrieb eines Mehrschichtaufbaus
US11560331B2 (en) * 2018-06-08 2023-01-24 Guardian Glass, LLC Coated glass article containing a semi-interpenetrating network

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4954591A (en) * 1987-11-06 1990-09-04 Pilkington Visioncare Holdings, Inc. Abrasion resistant radiation curable coating for polycarbonate article
US20040096666A1 (en) * 2002-11-14 2004-05-20 Knox Carol L. Photochromic article
US20050258408A1 (en) * 2001-12-20 2005-11-24 Molock Frank F Photochromic contact lenses and methods for their production
US20120121845A1 (en) * 2008-11-15 2012-05-17 Basf Coatings Gmbh High-transparency polycarbonates with scratch-resistant coating, process for production thereof and use thereof
WO2013148129A1 (fr) * 2012-03-26 2013-10-03 3M Innovative Properties Company Article et procédé de fabrication de celui-ci

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5149746A (en) * 1989-01-26 1992-09-22 The United States Of America As Represented By The National Aeronautics And Space Administration Semi-interpenetrating polymer network for tougher and more microcracking resistant high temperature polymers
US20120213969A1 (en) * 2011-02-18 2012-08-23 Syracuse University Functionally Graded Shape Memory Polymer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4954591A (en) * 1987-11-06 1990-09-04 Pilkington Visioncare Holdings, Inc. Abrasion resistant radiation curable coating for polycarbonate article
US20050258408A1 (en) * 2001-12-20 2005-11-24 Molock Frank F Photochromic contact lenses and methods for their production
US20040096666A1 (en) * 2002-11-14 2004-05-20 Knox Carol L. Photochromic article
US20120121845A1 (en) * 2008-11-15 2012-05-17 Basf Coatings Gmbh High-transparency polycarbonates with scratch-resistant coating, process for production thereof and use thereof
WO2013148129A1 (fr) * 2012-03-26 2013-10-03 3M Innovative Properties Company Article et procédé de fabrication de celui-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017130152B3 (de) 2017-12-15 2019-01-03 Acquandas GmbH Verfahren zum Betrieb eines Mehrschichtaufbaus
US11560331B2 (en) * 2018-06-08 2023-01-24 Guardian Glass, LLC Coated glass article containing a semi-interpenetrating network

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